1. Field of the Invention
The present invention relates to new anionic surfactants derived from aromatic or substituted aromatic molecules and alkene sulfonic acid. More particularly this invention relates to alkyl, dialkyl and higher substituted aromatic sulfonates and methods for preparing the substituted aromatic sulfonates wherein an aryl compound is alkylated and sulfonated in one step with an alkene sulfonic acid prior to neutralizing the acid.
The new surfactants and the new method to prepare them have the following advantages over existing aromatic sulfonate type surfactants:
1. Dialkyl and higher substituted aromatic sulfonates can be produced easily and in high yields. PA1 2. Alkoxylated aromatic sulfonates can be produced easily and in high yields. PA1 3. Mixed linear and branched substituted di-alkylaromatics can be produced easily and in high yields. PA1 4. Alkyl benzene sulfonates can be produced without using, presently costly, conventional alkylation processes. PA1 5. Sulfonated alkyl phenol alkoxylates can be produced without using, presently costly, conventional alkylation processes. PA1 6. The new surfactants possess a unique structure where the sulfonate group is attached to the end of one of the alkyl chains rather than to the aromatic ring. PA1 R'=none,alkyl(branched or linear C.sub.1 to C.sub.30 +) PA1 R"=none,alkyl(branched or linear C.sub.1 to C.sub.30 +) PA1 R'=none, alkyl(branched or linear C.sub.1 to C.sub.30 +) PA1 R"=none, alkyl(branched or linear C.sub.1 to C.sub.30 +) PA1 R'"=CH.sub.3 (CH.sub.2)nCH(CH).sub.2 mSO.sub.3 H
2. The Prior Art
Alkyl benzene sulfonates have been popular surfactants for a wide variety of detergent and industrial use. Beginning just after World War II, synthetic detergents based on the reaction of propylene tetramer and benzene using AlCl.sub.3 catalyst began to gain popularity and widespread use as laundry detergents. During the 1960s alkylbenzene sulfonates based on branched alkyl groups were found to be causing excessive foaming in sewage treatment plants and in rivers and lakes due to their slow biodegradability. Linear alkylbenzenes based on the reaction of linear olefins (U.S. Pat. No. 3,585,253 issued to Huang on Jun. 15, 1971) or linear chloroparaffins (U.S. Pat. No. 3,355,508 issued to Moulden on Nov. 28, 1967) were developed which gave acceptable detergency and were quickly biodegraded. Even more recently, the AlCl.sub.3 process has been replaced by the HF process and the Detal Process because of environmental objections to the AlCl.sub.3 process. Table 1 shows the typical yields obtained for detergent alkylates using HF catalyst.
TABLE 1 ______________________________________ Typical Yields of Detergent Alkylate (values in tons) Branched Alkylate Linear Alkylate ______________________________________ Material Charged Linear Paraffins -- 82.9 Benzene 39.9 34.3 Propylene tetramer 86.7 -- Total charged 126.6 117.3 Materials Produced Hydrogen -- 1.1 Light ends -- 3.8 HF regenerator bottoms 2.5 2.8 Light alkylate 8.0 -- Detergent alkylate 100.0 100.0 Heavy alkylate 16.1 9.6 Total produced 126.6 117.3 ______________________________________
Detergent use is the predominant market for alkylbenzenes and alkylbenzene sulfonates. These products; however; are also employed in considerable quantities as lubricants, coolants, industrial surfactants, dispersants, emulsifiers, corrosion inhibitors, demulsifiers and for many other uses. They find widespread use in many industries among which are petroleum recovery, refining, emulsion polymerization, textile dyeing, agriculture, industrial and institutional cleaning, drilling fluids, paper processing, coatings, and adhesives.
Present processes are designed to optimize the yields of detergent alkylate (predominantly monoalkylbenzene). The yields of heavy alkylate (predominantly dialkylbenzene) are therefore low. These heavy alkylates however find considerable demand as oil soluble surfactants and specialty chemicals. Dialkylbenzene sulfonates (U.S. Pat. No. 4,004,638 issued to Burdyn, Chang and Cook on Jan. 25,1977, U.S. Pat. No. 4,536,301 issued to Malloy and Swedo on Aug. 20, 1985), alkyl xylene sulfonates (EP121964) and dialkyl phenol polyethoxy alkyl sulfonates (U.S. Pat. No. 4,220,204 issued to Hughes, Kudchadker and Dunn on Sep. 2, 1980) have all been used to increase the productivity of crude oil; however; the availability of these materials has been limited until this invention because of the low yields of heavy alkylates available for conversion to their corresponding sulfonates. In addition no commercially feasible process is available, until this invention, for producing di- and tri- alkylbenzenes where both linear and branched alkyl groups are present on the same benzene ring.
Alkoxylated Alkyl Substituted Phenol Sulfonates have been produced and found to be useful as surfactants in numerous applications. U.S. Pat. No. 5,049,311 issued to Rasheed, Cravey, Berger and O'Brien on Sep. 17, 1991, lists many uses for these compounds including surfactants for Enhanced Oil Recovery, corrosion inhibitors, hydrotropes, foaming agents in concrete formation, surfactants for dye carriers, surfactants for fiber lubricants, surfactants for emulsion polymerization, textile detergents, foaming agents for drilling fluids, and agricultural emulsifiers.